Agent for coloring keratin fibres

ABSTRACT

The agent for coloring keratin fibers is free of chemical oxidants, is in the form of an aqueous or aqueous-alcoholic dye-containing preparation, and contains a combination of oxidation dyes and at least three direct dyes. The agent is characterized by a quantitative ratio of oxidation dyes to direct dyes equal to 5:1 to 0.5:1. A method of dyeing hair is described in which the agent is applied to hair and allowed to act on the hair for an acting time of 5 to 60 minutes without addition of chemical oxidants, so that air oxidation provides a uniform and stable coloration of the hair.

CROSS-REFERENCE

This is the US National Stage of PCT/EP 2004/007366, filed on Jul. 6,2004 in Europe.

BACKGROUND OF THE INVENTION

1. The Field of the Invention

The present invention relates to compositions for coloring keratinfibers, particularly human hair, based on a developer-couplercombination and direct dyes which compositions make it possible toimpart to the fibers a lasting coloration without the addition of anoxidant (comparable to the sta-bility of semipermanent colors) while atthe same time causing only minor damage to the fibers (comparable totemporary hair dyes).

2. The Related Art

In the field of keratin fiber coloring, particularly hair coloring,oxidation dyes have attained substantial importance. The coloration isformed by reaction of certain developers with certain couplers in thepresence of a suitable oxidant. For very gentle uses, however, the needexists for colorants which in the presence of atmospheric oxygen givelasting colorations even without the addition of an oxidant.

It is known from EP 1 166 748 A2 that the combination of oxidation dyesand optionally direct dyes can be used for hair dyeing without theaddition of a chemical oxidant. Constant coloring results (namely acoloration that is the same immediately after the use as well as days orweeks thereafter) are not possible with the agents described in thatdocument.

SUMMARY OF THE INVENTION

The purpose of the present invention therefore is to provide an agentwhich upon air oxidation does not develop the coloration only afterdays, but does so immediately after application giving a uniformcoloration which remains virtually constant over a period of up to 20hair washings.

Surprisingly, we have now found that by use of a special combination ofoxidation dyes and direct dyes, the combination containing at leastthree direct dyes and the quantitative ratio of oxidation dyes to directdyes being 5:1 to 0.5:1, it is possible to obtain outstanding coloringresults characterized by a natural luster and a long-lasting uniformcoloration without the original coloration undergoing a color change.The agent of the invention colors the hair in very gentle manner(comparable to the conventionally used readily washed out tintingagents) so that the hair remains practically undamaged. The object ofthe invention provides a constant coloration which lasts over a periodof up to 20 washings of the colored hair.

The object of the invention therefore is an agent for coloring keratinfibers, particularly human hair, which is free of chemical oxidants andis characterized in that it is in the form of an aqueous oraqueous-alcoholic preparation and contains a combination of oxidationdyes (developers, couplers) and direct dyes, said combination containingat least three direct dyes, and that the quantitative ratio of oxidationdyes to direct dyes equals 5:1 to 0.5:1.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Suitable oxidation dye precursors are, for example, the followingdevelopers and couplers and self-coupling compounds:

-   (i) Developers: 1,4-diaminobenzene(p-phenylenediamine),    1,4-diamino-2-methylbenzene (p-toluylenediamine),    1,4-diamino-2,6-dimethylbenzene, 1,4-diamino-3,5-diethylbenzene,    1,4-diamino-2,5-dimethylbenzene, 1,4-diamino-2,3-dimethylbenzene,    2-chloro-1,4-diaminobenzene, 1,4-diamino-2-(thiophen-2-yl)benzene,    1,4-diamino-2-(thiophen-3-yl)benzene,    1,4-diamino-2-(pyridin-3-yl)-benzene, 2,5-diaminobiphenyl,    1,4-diamino-2-methoxymethylbenzene,    1,4-diamino-2-aminomethylbenzene,    1,4-diamino-2-hydroxymethylbenzene,    1,4-diamino-2-(2-hydroxyethoxy)benzene,    2-[(2-acetylamino)ethoxy]-1,4-diaminobenzene, 4-phenylaminoaniline,    4-dimethylaminoaniline, 4-diethylaminoaniline,    4-dipropylaminoaniline, 4-[ethyl(2-hydroxyethyl)amino]aniline,    4-[di(2-hydroxyethyl)amino]aniline,    4-[di(2-hydroxyethyl)amino-2-methylaniline,    4-[(2-methoxyethyl)amino]aniline, 4-[(3-hydroxypropyl)amino]aniline,    4-[(2,3-dihydroxypropyl)amino]aniline,    1,4-diamino-2-(2-hydroxyethyl)benzene,    1,4-diamino-2-(1-methylethyl)benzene,    1,3-bis[(4-aminophenyl)(2-hydroxyethyl)amino]-2-propanol,    1,4-bis[(4-aminophenyl)amino]butane,    1,8-bis(2,5-diaminophenoxy)-3,6-dioxaoctane, 4-aminophenol,    4-amino-3-methylphenol, 4-amino-3-(hydroxymethyl)phenol,    4-amino-3-fluorophenol, 4-methylaminophenol,    4-amino-2-(aminomethyl)phenol, 4-amino-2-(hydroxymethyl)phenol,    4-amino-2-fluorophenol,    4-amino-2-[(2-hydroxyethyl)amino]methylphenol,    4-amino-2-methylphenol, 4-amino-2-(methoxymethyl)phenol,    4-amino-2-(2-hydroxyethyl)phenol, 5-amino-salicylic acid,    2,5-diaminopyridine, 2,4,5,6-tetraminopyrimidine,    2,5,6-triamino-4-(1H)-pyrimidone,    4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazole,    4,5-diamino-1-(1-methylethyl)-1H-pyrazole,    4,5-diamino-1-[(4-methylphenyl)methyl]-1H-pyrazole,    1-[(4-chlorophenyl)methyl]-4,5-diamino-1H-pyrazole,    4,5-diamino-1-methyl-1H-pyrazole, 2-aminophenol,    2-amino-6-methylphenol and 2-amino-5-methylphenol, alone or in    admixture with one another.-   (ii) Couplers: N-(3-Dimethylaminophenyl)urea, 2,6-diaminopyridine,    2-amino-4-[(2-hydroxyethyl)amino]anisole,    2,4-diamino-1-fluoro-5-methylbenzene,    2,4-diamino-1-methoxy-5-methylbenzene,    2,4-diamino-1-ethoxy-5-methylbenzene,    2,4-diamino-1-(2-hydroxyethoxy)-5-methylbenzene,    2,4-di[(2-hydroxyethyl)amino-1,5-dimethoxybenzene,    2,3-diamino-6-methoxypyridine,    3-amino-6-methoxy-2-(methylamino)pyridine,    2,6-diamino-3,5-dimethoxypyridine,    3,5-diamino-2,6-dimethoxy-pyridine, 1,3-diaminobenzene,    2,4-diamino-1-(2-hydroxyethoxy)benzene,    1,3-diamino-4-(2,3-dihy-droxypropoxy)benzene,    2,4-diamino-1,5-di(2-hydroxyethoxy)benzene,    1-(2-aminoethoxy)-2,4-di-aminobenzene,    2-amino-1-(2-hydroxyethoxy)-4-methylaminobenzene,    2,4-diaminophenoxyacetic acid, 3-[di(2-hydroxyethyl)amino]aniline,    4-amino-2-di[(2-hydroxyethyl)amino]-1-ethoxybenzene,    5-methyl-2-(1-methylethyl)phenol, 3-[(2-hydroxyethyl)amino]aniline,    3-[(2-aminoethyl)amino]aniline, 1,3-di(2,4-diaminophenoxy)propane,    di(2,4-diaminophenoxy)methane, 1,3-diamino-2,4-dimethoxy-benzene,    2,6-bis(2-hydroxyethyl)aminotoluene, 4-hydroxyindole,    3-dimethylaminophenol, 3-dieth-ylaminophenol,    5-amino-2-methylphenol, 5-amino-4-fluoro-2-methylphenol,    5-amino-4-methoxy-2-methylphenol, 5-amino-4-ethoxy-2-methylphenol,    3-amino-2,4-dichlorophenol, 5-amino-2,4-dichlo-rophenol,    3-amino-2-methylphenol, 3-amino-2-chloro-6-methylphenol,    3-aminophenol, 2-[(3-hydroxyphenyl)amino]acetamide,    5-[(2-hydroxyethyl)amino]-4-methoxy-2-methylphenol,    5[(2-hydroxyethyl)amino]-2-methylphenol,    3[(2-hydroxyethyl)amino]phenol, 3-[(2-methoxyethyl)amino]phenol,    5-amino-2-ethylphenol, 5-amino-2-methoxyphenol,    2-(4-amino-2-hydroxyphenoxy)ethanol,    5-[(3-hydroxypropyl)amino]-2-methylphenol,    3-[(2,3-dihydroxypropyl)amino]-2-methylphenol,    3-[(2-hydroxyethyl)amino]-2-methylphenol, 2-amino-3-hydroxypyridine,    5-amino-4-chloro-2-methylphenol, 1-naphthol, 2-methyl-1-naphthol,    1,5-dihydroxynaphthalene, 1,7-dihydroxynaphthalene,    2,3-dihydroxynaphthalene, 2,7-dihydroxynaphthalene,    2-methyl-1-naphthol acetate, 1,3-dihydroxybenzene,    1-chloro-2,4-dihydroxybenzene, 2-chloro-1,3-dihydroxybenzene,    1,2-dichloro-3,5-dihydroxy-4-methylbenzene,    1,5-dichloro-2,4-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene,    3,4-methylenedioxyphenol, 3,4-methylenedioxyaniline,    5-[(2-hydroxyethyl)amino]-1,3-benzodioxol,    6-bromo-1-hydroxy-3,4-methylenedioxybenzene, 3,4-diaminobenzoic    acid, 3,4-dihydro-6-hydroxy-1,4(2H)-benzoxazine,    6-amino-3,4-dihydro-1,4(2H)-benzoxazine,    3-methyl-1-phenyl-5-pyrazolone, 5,6-dihydroxyindole,    5,6-dihydroxyindoline, 5-hydroxyindole, 6-hydroxyindole,    7-hydroxyindole and 2,3-indolinedione, alone or in admixture with    one another.-   (iii) Self-coupling compounds: 2-amino-5-methylphenol,    2-amino-6-methylphenol, 2-amino-6-ethoxyphenol or    2-propylamino-5-aminopyridine.

Among the afore-indicated oxidation dyes, the following compounds, aloneor in combination with one another, are particularly preferred:

-   2,5-diaminotoluene, 2,4-diaminophenoxyethanol, resorcinol,    2-methylresorcinol, m-aminophenol, 4-amino-3-methylphenol,    4-amino-2-hydroxytoluene, 6-amino-3-methylphenol,    2-amino-4-hydroxyethylaminoanisole, 1-naphthol,    hydroxyethyl-3,4-methylenedioxyaniline, 2,5-diaminophenylethanol,    N,N-bis(2-hydroxyethyl)-p-phenylenediamine, phenylmethylpyrazolone,    1-hydroxyethyl-4,5-diaminopyrazole and    2-amino-6-chloro-4-nitrophenol or the salts thereof.

The total amount of oxidation dye precursors contained in the agent ofthe invention is about 0.01 to 12 weight percent and particularly about0.1 to 7 weight percent. Particularly preferred dyes are listed in Table1.

Suitable direct dyes are all common natural and/or synthetic directdyes, for example the vegetable dyes such as henna or indigo,triphenylmethane dyes, aromatic nitro dyes, azo dyes, quinone dyes andcationic or anionic dyes.

Suitable synthetic dyes are, for example:

-   1,4-bis[(2-hydroxyethyl)amino]-2-nitrobenzene,    1-(2-hydroxyethyl)amino-2-nitro-4-[di(2-hydroxyethyl)amino]benzene    (HC Blue No. 2),    1-amino-3-meth-yl-4-[(2-hydroxyethyl)amino]-6-nitrobenzene (HC    Violet No. 1),    4-[ethyl-(2-hydroxyethyl)amino]-1-[(2-hydroxyethyl)amino]-2-nitrobenzene    hydrochloride (HC Blue No. 12),    4-[di(2-hydro-xyethyl)amino]-1-[(2-methoxyethyl)amino]-2-nitrobenzene    (HC Blue No. 11),    1-[(2,3-dihydroxy-propyl)amino]-4-[methyl-(2-hydroxyethyl)amino]-2-nitrobenzene    (HC Blue No. 10),    1-[(2,3-dihy-droxypropyl)amino]-4-[ethyl-(2-hydroxyethyl)amino]-2-nitrobenzene    hydrochloride (HC Blue No. 9),    1-(3-hydroxypropylamino)-4-[di(2-hydroxyethyl)amino]-2-nitrobenzene    (HC Violet No. 2),    1-meth-ylamino-4-[methyl-(2,3-dihydroxypropyl)amino]-2-nitrobenzene    (HC Blue No. 6),    2-[(4-amino-2-nitrophenyl)amino]-5-dimethylaminobenzoic acid (HC    Blue No. 13), 1-amino-4-[(2-hydroxy-ethyl)amino]-2-nitrobenzene (HC    Red No. 7), 2-amino-4,6-dinitrophenol, 4-amino-2-nitrodiphenylamine    (HC Red No. 1), 1-amino-4-[di(2-hydroxyethyl)amino]-2-nitrobenzene    hydrochloride (HC Red No. 13),    1-amino-5-chloro-4-[(2-hydroxyethyl)amino]-2-nitrobenzene,    4-amino-1-[(2-hydroxyethyl)amino]-2-nitrobenzene (HC Red No. 3),    4-amino-3-nitrophenol, 4-[(2-hydroxyethyl)amino]-3-nitrophenol,    1-[(2-aminoethyl)amino]-4-(2-hydroxyethoxy)-2-nitrobenzene (HC    Orange No. 2),    4-(2,3-dihydroxypropoxy)-1-[(2-hydroxyethyl)amino]-2-nitrobenzene    (HC Orange No. 3),    1-amino-5-chloro-4-[(2,3-dihydroxypropyl)amino]-2-nitrobenzene (HC    Red No. 10),    5-chloro-1,4-[di(2,3-dihydroxypropyl)amino]-2-nitrobenzene (HC Red    No. 11), 2-[(2-hydroxyethyl)amino]-4,6-dinitrophenol,    4-ethylamino-3-nitrobenzoic acid,    2-[(4-amino-2-nitrophenyl)-amino]benzoic acid,    2-chloro-6-ethylamino-4-nitrophenol, 2-amino-6-chloro-4-nitrophenol,    4-[(3-hydroxypropyl)amino]-3-nitrophenol,    2,5-diamino-6-nitropyridine, 1,2,3,4-tetrahydro-6-nitroquinoxaline,    7-amino-3,4-dihydro-6-nitro-2H-1,4-benzoxazine, (HC Red. No. 14),    1-amino-2-[(2-hydroxyethyl)amino]-5-nitrobenzene (HC Yellow No. 5),    1-(2-hydroxyethoxy)-2-[(2-hydroxyethyl)amino]-5-nitrobenzene (HC    Yellow No. 4), 1-[(2-hydroxyethyl)amino]-2-nitrobenzene (HC Yellow    No. 2), 2-[(2-hydroxyethyl)amino]-1-methoxy-5-nitrobenzene,    2-amino-3-nitrophenol,    1-(2-hydroxyethoxy)-3-methylamino-4-nitrobenzene,    2,3-(dihydroxypropoxy)-3-methylamino-4-nitroben-zene,    2-[(2-hydroxyethyl)amino]-5-nitrophenol (HC Yellow No. 11),    3-[(2-aminoethyl)amino]-1-methoxy-4-nitrobenzene hydrochloride (HC    Yellow No. 9), 1-[(2-ureidoethyl)amino]-4-nitro-benzene,    4-[(2,3-dihydroxypropyl)amino]-3-nitro-1-trifluoromethylbenzene (HC    Yellow No. 6),    1-chloro-2,4-bis[(2-hydroxyethyl)amino]-5-nitrobenzene (HC Yellow    No. 10), 4-[(2-hydro-xyethyl)amino]-3-nitro-1-methylbenzene,    1-chloro-4-[(2-hydroxyethyl)amino]-3-nitrobenzene (HC Yellow No.    12), 4-[(2-hydroxyethyl)amino]-3-nitro-1-trifluoromethylbenzene (HC    Yellow No. 13), 4-[(2-hydroxyethyl)amino]-3-nitrobenzonitrile (HC    Yellow No. 14), 4-[(2-hydroxyethyl)amino]-3-nitrobenzamide (HC    Yellow No. 15),    1,4-di[(2,3-dihydroxypropyl)amino]-9,10-anthraquinone,    1-[(2-hydroxyethyl)amino]-4-methylamino-9,10-anthraquinone (CI    61505, Disperse Blue No. 3),    2-[(2-aminoethyl)amino]-9,10-anthraquinone (HC Orange No. 5),    1-hydroxy-4-[(4-methyl-2-sulfophenyl)-amino]-9,10-anthraquinone,    1-[(3-aminopropyl)amino]-4-methylamino-9,10-anthraquinone (HC Blue    No. 8), 1-[(3-aminopropyl)amino]-9,10-anthraquinone (HC Red No. 8),    1,4-diamino-2-meth-oxy-9,10-anthraquinone (CI 62015, Disperse Red    No. 11), Solvent Violet No. 26),    1,4-dihydroxy-5,8-bis[2-hydroxyethyl)amino]-9,10-anthraquinone (CI    62500, Disperse Blue No. 7, Solvent Blue No. 69),    9-(dimethylamino)benzo[a]-phenoxazin-7-ium chloride (CI 51175; Basic    Blue No. 6),    di[4-(diethylamino)phenyl][4-(ethylamino)naphthyl]carbenium chloride    (CI 42595; Basic Blue No. 7),    3,7-di(dimethylamino)phenothiazin-5-ium chloride (CI 52015; Basic    Blue No. 9),    di[4-(dimethylamino)phenyl][4-(phenylamino)naphthyl]carbenium    chloride (CI 44045; Basic Blue No. 26),    2-{[4-(ethyl(2-hydroxyethyl)amino)phenyl]azo}-6-methoxy-3-methylbenzothiazolium    methylsul-fate (CI 11154; Basic Blue No. 41),    8-amino-2-bromo-5-hydroxy-4-imino-6-{[3-(trimethyl-ammonio)phenyl]amino}-1(4H-naphthalenone    chloride (CI 56059; Basic Blue No. 99),    bis[4-(dimethylamino)phenyl][4-(methylamino)phenyl]carbenium    chloride (CI 42535; Basic Violet No. 1),    tris[4-(dimethylamino)phenyl]carbenium chloride (CI 42555; Basic    Violet No. 3), 2-[3,6-(diethylamino)dibenzopyranium-9-yl]benzoyl    chloride (CI 45170; Basic Violet No. 10),    di(4-aminophenyl)(4-amino-3-methylphenyl)carbenium chloride (CI    42510, Basic Violet No. 14),    1,3-bis[(2,4-diamino-5-methylphenyl)azo]-3-methylbenzene (CI 21010;    Basic Brown No. 4),    1-[(4-aminophenyl)azo]-7-(trimethylammonio)-2-naphthol chloride (CI    12250; Basic Brown No. 16),    1-[(4-amino-2-nitrophenyl)azo]-7-(trimethylammonio-2-naphthol    chloride (Basic Brown No. 17),    1-[(4-amino-3-nitrophenyl)azo]-7-(trimethylammonio)-2-naphthol    chloride (CI 12251; Basic Brown No. 17 [sic]),    3,7-diamino-2,8-dimethyl-5-phenylphenazinium chloride (CI 50240;    Basic Red No. 2),    1,4-dimethyl-5-{[(4-(dimethylamino)phenyl]azo}-1,2,4-triazolium    chloride (CI 11055; Basic Red No. 22),    2-hydroxy-1-[(2-methoxyphenyl)azo]-7-(trimethylammonio)naphthalene    chloride (CI 12245; Basic Red No. 76),    2-{2-[(2,4-dimethoxyphenyl)amino]ethenyl}-1,3,3-trimethyl-3H-indol-1-ium    chloride (CI 48055; Basic Yellow No. 11),    3-methyl-1-phenyl-4-{[3-(trimethylammonio)phenyl]azo}pyrazol-5-one    chloride (CI 12719; Basic Yellow No. 57),    bis[4-(diethylamino)phenyl]phenylcarbenium hydrogen sulfate (1:1)    (CI 42040; Basic Green No. 1),    1-[di(2-hydroxyethyl)amino]-3-methyl-4-[(4-nitrophenyl)azo]benzene    (CI 11210; Disperse Red No. 17),    4-[(4-aminophenyl)azo]-1-[di(2-hydroxyethyl)amino]-3-methylbenzene    (HC Yellow No. 7), 2,6-diamino-3-[(pyridin-3-yl)azo]pyridine,    6-hydroxy-5-[(4-sulfophenyl)azo]-2-naphthalenesulfonic acid disodium    salt (CI 15985; Food Yellow No. 3; FD&C Yellow No. 6),    2,4-dinitro-1-naphthol-7-sulfonic acid disodium salt (CI 10316; Acid    Yellow No. 1; Food Yellow No. 1),    2-(indan-1,3-dion-2-yl)-quinoline-x,x-sulfonic acid (mixture of    mono- and disulfonic acid) (CI 47005; D&C Yellow No. 10; Food Yellow    No. 13; Acid Yellow No. 3),    5-hydroxy-1-(4-sulfophenyl)-4-[(4-sulfophenyl)azo]-pyrazole-3-carboxylic    acid trisodium salt (CI 19140; Food Yellow No. 4; Acid Yellow No.    23), 9-(2-carboxyphenyl)-6-hydroxy-3H-xanthen-3-one (CI 45350; Acid    Yellow No. 73; D&C Yellow No. 8),    5-[(2,4-dinitrophenyl)amino]-2-phenylaminobenzenesulfonic acid    sodium salt (CI 10385; Acid Orange No. 3),    4-[(2,4-dihydroxyphenyl)azo]benzenesulfonic acid monosodium salt (CI    14270; Acid Orange No. 6),    4-[(2-hydroxynaphth-1-yl)azo]benzenesulfonic acid sodium salt (CI    15510; Acid Orange No. 7),    4-[(2,4-dihydroxy-3-[(2,4-dimethylphenyl)azo]phenyl)azo]benzenesulfonic    acid sodium salt (CI 20170; Acid Orange No. 24),    4-hydroxy-3-[(4-sulfonaphth-1-yl)azo]-1-naphthalenesulfonic acid    disodium salt (CI 14720; Acid Red No. 14),    6-hydroxy-5-[(4-sulfonaphth-1-yl)azo]-2,4-naphthalenedisulfonic acid    trisodium salt (CI 16255; Ponceau 4R; Acid Red No. 18),    3-hydroxy-4-[(4-sulfonaphth-1-yl)azo]-2,7-naphthalenedisulfonic acid    trisodium salt (CI 16185; Acid Red No. 27),    8-amino-1-hydroxy-2-(phenylazo)-3,6-naphthalenedisulfonic acid    disodium salt (CI 17200; Acid Red No. 33),    5-(acetylamino)-4-hydroxy-3-[(2-methylphenyl)azo]-2,7-naphthalenedisulfonic    acid disodium salt (CI 18065; Acid Red No. 35),    2-(3-hydroxy-2,4,5,7-tetraiododibenzopyran-6-on-9-yl)benzoic acid    disodium salt (CI 45430; Acid Red No. 51),    N-[6-(diethylamino)-9-(2,4-disulfophenyl)-3H-xanthen-3-ylidene]-N-ethylethanammonium    hydroxide, inner salt, sodium salt (CI 45100; Acid Red No. 52),    8-{[4-(phenylazo)phenyl]azo}-7-naphthol-1,3-disulfonic acid disodium    salt (CI 27290; Acid Red No. 73),    2′,4′,5′,7′-tetrabromo-3′,6′-dihydroxyspiro[isobenzofuran-1(3H),    9′-[9H]-xanthen]-3-one disodium salt (CI 45380; Acid Red No. 87),    2′,4′,5′,7′-tetrabromo-4,5,6,7-tetrachloro-3′,6′-dihydroxyspiro[isobenzofuran-1    (3H), 9′-[9H]-xanthen]-3-one disodium salt (CI 45410; Acid Red No.    92), 3′,6′-dihydroxy-4′,5′-diiodispiro[isobenzofuran-1(3H),    9′(9H)xanthen]-3-one disodium salt (CI 45425; Acid Red No. 95),    (2-sulfophenyl)di[4-(ethyl-((4-sulfophenyl)methyl)amino)phenyl]carbenium    disodium salt betaine (CI 42090; Acid Blue No. 9; FD&C Blue No. 1),    1,4-bis[(2-sulfo-4-methylphenyl)amino]-9,10-anthraquinone disodium    salt (CI 61570; Acid Green No. 25),    bis[4-(dimethylamino)phenyl]-3,7-disulfo-2-hydroxynaphth-1-yl)car-benium    inner salt, monosodium salt (CI 44090; Food Green No. 4; Acid Green    No. 50), bis[4-(di-ethylamino)phenyl][2,4-disulfophenyl)carbenium    inner salt, sodium salt (2:1) (CI 42045; Food Blue No. 3; Acid Blue    No. 1),    bis[4-(diethylamino)phenyl](5-hydroxy-2,4-disulfophenyl)carbenium    inner salt, calcium salt (2:1) (CI 42051; Acid Blue No. 3),    1-amino-4-(cyclohexylamino)-9,10-anthra-quinone-2-sulfonic acid    sodium salt (CI 62045; Acid Blue No. 62),    2-(1,3-dihydro-3-keto-5-sulfo-2H-indol-2-ylidene)-2,3-dihydro-3-keto-1H-indole-5-sulfonic    acid disodium salt (CI 73015; Acid Blue No. 74),    9-(2-carboxyphenyl)-3-[(2-methylphenyl)amino]-6-[(2-methyl-4-sulfophenyl)amino]-xanthylium    inner salt, monosodium salt (CI 45190; Acid Violet No. 9),    1-hydroxy-4-[(4-methyl-2-sulfophenyl)amino]-9,10-anthraquinone    sodium salt (CI 60730; D&C Violet No. 2; Acid Violet No. 43),    bis{3-nitro-4-[(4-phenylamino)-3-sulfophenylamino]phenyl}sulfone (CI    10410; Acid Brown No. 13),    5-amino-4-hydroxy-6-[(4-nitrophenyl)azo]-3-(phenylazo)-2,7-naphthalenedisulfonic    acid diso-dium salt (CI 20470; Acid Black No. 1),    3-hydroxy-4-[(2-hydroxynaphth-1-yl)azo]-7-nitro-1-naph-thalenesulfonic    acid chromium complex (3:2) (CI 15711; Acid Black No. 52),    3-[(2,4-dimethyl-5-sulfophenyl)azo]-4-hydroxy-1-naphthalenesulfonic    acid disodium salt (CI 14700; Food Red No. 1; FD&C Red No. 4),    4-(acetylamino)-5-hydroxy-6-[(7-sulfo-4-[(4-sulfophenyl)azo]naphth-1-yl)azo]-1,7-naphthalenedisulfonic    acid tetrasodium salt (CI 28440; Food Black No. 1) and    3-hydroxy-4-(3-methyl-5-keto-1-phenyl-4,5-dihydro-1H-pyrazol-4-ylazo)naphthalene-1-sulfonic    acid sodium salt, chromium complex (Acid Red No. 195), alone or in    combination with one another.

Among the aforesaid direct dyes, the following compounds—alone or incombination with one another—are particularly preferred:

-   hydroxyethyl-2-nitro-p-toluidine, 2-hydroxyethylpicramic acid,    4-nitrophenylaminourea, tri(4-amino-3-methylphenyl)carbenium    chloride (Basic Violet 2), 1,4-di-amino-9,10-anthracenedione    (Disperse Violet 1),    1-(2-hydroxyethyl)amino-2-nitro-4-[di(2-hydroxy-ethyl)amino]benzene    (HC Blue No. 2),    4-[ethyl-(2-hydroxyethyl)amino]-1-[(2-hydroxyethyl)amino]-2-nitrobenzene    hydrochloride (HC Blue No. 12),    1-amino-4-[di(2-hydroxyethyl)amino]-2-nitro-benzene hydrochloride    (HC Red No. 13),    3-{[2-nitro-4-(trifluoromethyl)phenyl]amino}-1,2-propanediol (HC    Yellow No. 6), 4-amino-1[(2-hydroxyethyl)amino]-2-nitrobenzene (HC    Red No. 3), 4-amino-3-nitrophenol,    4[(2-hydroxyethyl)amino]-3-nitrophenol,    1-amino-5-chloro-4-[di(2,3-dihydroxypropyl)amino]-2-nitrobenzene (HC    Red No. 10,    5-chloro-1,4-[di(2,3-dihydroxypropyl)amino]-2-nitrobenzene (HC Red    No. 11), 2-chloro-6-ethylamino-4-nitrophenol,    2-amino-6-chloro-4-nitrophenol,    4-[(2-hydroxyethyl)amino]-3-nitro-1-trifluoromethylbenzene (HC    Yellow No. 13),    8-amino-2-bromo-5-hydroxy-4-imino-6-{[3-(trimethylammonio)phenyl]amino}-1(4H]-naphthalenone    chloride (CI 56059; Basic Blue No. 99),    1-[(4-aminophenyl)azo]-7-(trimethylammonio)-2-naphthol chloride (CI    12250; Basic Brown No. 16),    1-[(4-amino-2-nitrophenyl)azo]-7-(trimethylammonio)-2-naphthol    chloride (Basic Brown No. 17),    2-hydroxy-1-[(2-methoxyphenyl)azo]-7-(trimethylammonio)naphthalene    chloride (CI 12245; Basic Red No, 76),    3-methyl-1-phenyl-4-{[3-(trimethylammonio)phenyl]azo}pyrazol-5-one    chloride (CI 12719; Basic Yellow No. 570 and    2,6-diamino-3-[(pyridin-3-yl)azo]pyridine and the salts thereof.

The total amount of direct dyes in the agent of the invention is about0.01 to 7 weight percent and preferably about 0.2 to 4 weight percent.Particularly preferred dyes are listed in Table 1.

Other known and common dyes that can be contained in the coloring agentof the invention are described in, among other publications, E. Sagarin“Cosmetics, Science and Technology”, Interscience Publishers Inc., NewYork (1957), pages 503 ff, in H. Janistyn “Handbuch der Kosmetika undRiechstoffe” [Handbook of Cosmetics and Perfumes], vol. 3 (1973), pages388 ff, and in K. Schrader “Grundlagen und Rezepturen der Kosmetika”[Fundamentals and Formulations of Cosmetics], 2nd edition (1989), pages782-815, which in particular are included herein by reference.

In addition, the agent of the invention can contain antioxidants, forexample ascorbic acid, thioglycolic acid or sodium sulfite, as well ascomplexing agents for heavy metals, for example an ethylenediaminetetraacetate, or nitriloacetic acid, in an amount of up to about 0.5weight percent. The colorant carrier composition can contain perfumeoils in an amount of up to about 1 weight percent. Naturally, theafore-described hair colorant can optionally contain other additivescommonly employed in hair colorants, such as, for example, thickeners,for example homopolymers of acrylic acid, vegetable gums, cellulosederivatives and starch derivatives, algal polysaccharides, amphiphilicassociative thickeners, furthermore preservatives; complexing agents,solvents such as water, lower aliphatic alcohols, for example aliphaticalcohols with 1 to 4 carbon atoms, such as ethanol, propanol, andisopropanol, or glycols such as glycerol and 1,2-propylene glycol,wetting agents or emulsifiers from the classes of anionic, cationic,amphoteric or nonionic surfactants; furthermore softeners; vaselines;silicone oils, paraffin oil, polysorbates and fatty acids as well ashair-care agents such as cationic polymers or resins, lanolinderivatives, cholesterol, vitamins, pantothenic acid and betaine. Thesaid constituents are used in amounts usually employed for suchpurposes, for example the wetting agents and emulsifiers at aconcentration from 0.1 to 30 weight percent and the hair-care agents ata concentration from 0.1 to 5.0 weight percent.

The pH of the colorant of the invention is in the range of about 5 to 11and preferably 7 to 9.

Depending on the composition and the desired pH of the colorant, the pHis preferably adjusted with an organic amine, for example a glucamine,aminomethylpropanol, monoethanolamine or triethanolamine, but ammonia oran inorganic base, for example sodium hydroxide, potassium hydroxide,sodium carbonate or calcium hydroxide, or an organic acid or inorganicacid, such as, for example, lactic acid, citric acid, acetic acid orphosphoric acid, can also be used. The agent of the invention is appliedto dry or previously washed fibers and after an exposure time of 5 to 60minutes and preferably after 10 to 45 minutes it is rinsed out withwater and optionally washed out with a shampoo. The keratin fibers canthen optionally be post-treated in the usual manner and dried.

Another object is the use of an aqueous or aqueous-alcoholic preparationcontaining a combination of oxidation dyes and direct dyes, whereinthere are present at least three direct dyes and the quantitative ratioof oxidation dyes to direct dyes equals 5:1 to 0.5:1, for thepreparation of an agent for coloring keratin fibers, said agent beingfree of chemical oxidants and upon air oxidation (namely without theaddition of a chemical oxidant) gives a uniform and stable colorationimmediately after use.

The following examples will explain in greater detail the object of theinvention without limiting it to the examples:

EXAMPLES Example 1

Aerosol Colorant in Cream Form 1.2 g of cetylstearyl alcohol 0.6 g ofsodium laurylsulfate 0.1 g of disodium ethylenediaminetetraacetate 0.2 gof ascorbic acid 2.5 g of 1,2-propylene glycol 2.5 g of ethanol 4.5 g ofammonia 2.5 g of monoethanolamine 1.3 g of 2,5-diaminotoluene sulfate0.7 g of 5-amino-2-methylphenol 1.3 g of2,2′-((4-((2-hydroxyethyl)amino]imino- 3-nitrophenyl)}bis-ethanol (HCBlue No. 2) 0.5 g of 2-[(4-amino-2-nitrophenyl)amino)-3-nitrophenyl)imino)ethanol (HC Red No. 3) 0.6 g of3-(4-amino-2-chloro-5-nitrophenyl)amino- 1,2-propanediol (HC Red No.10 + 11) 0.3 g of perfume oil to 100.0 g water

The dye compositions prepared by the hot emulsification method wereintroduced into appropriate compressed-gas containers withpropane/butane and F 152 (1:1 ratio) in an active ingredient/propellantgas ratio of 95:5%.

The aerosol foam was applied to dry hair and after an exposure time of20 minutes rinsed out with water. The hair was then dried. This gave alustrous red-brown coloration.

Example 2

Aerosol Colorant in Gel Form 2.00 g of hydroxyethylcellulose 20.00 g ofcocamidopropylbetaine 1.50 g of D-panthenol 10.00 g of ethanol 0.10 g ofdisodium tetraborate 0.10 g of disodium ethylenediaminetetraacetate 0.20g of ascorbic acid 4.50 g of monoethanolamine 2.00 g of2,5-diaminotoluene sulfate 0.75 g of resorcinol 0.70 g of2-amino-4-(2′-hydroxyethylamino)anisole 0.35 g of 3-aminophenol 3.10 gof (4-ethyl((2-hydroxyethyl)amino)-2- nitrophenyl)amino}ethanol hydro-chloride (HC Blue No. 12) 1.00 g of3-{[2-nitro-4-(trifluoromethyl)phenyl]amino}- 1,2-propanediol (HC YellowNo. 6) 1.00 g of 3-[(4,5-dihydro-3-methyl-5-keto-1-phenyl-1H-pyrazol-4-yl)azo]-N,N,N-tri- methylbenzenaminium chloride(Basic Yellow No. 57) 0.47 g of 1,4-diamino-9,10-anthracenedione(Disperse Violet No. 1) 0.70 g of1-N-hydroxyethylamino-4-methyl-2-nitrobenzene 3.10 g of sodiumhydroxide, 20% aqueous solution 0.50 g of perfume oil to 100.00 g water

The gel base prepared by the cold-mixing method was combined withhot-dissolved dyes and introduced into an appropriate compressed-gascontainer with propane/butane and F 152 (1:1 ratio) in an activeingredient/propellant gas ratio of 95:5%.

The aerosol foam was applied to washed hair and after an exposure timeof 15 minutes rinsed out with water. The hair was then washed with agentle shampoo, again rinsed with water and then dried. This gave alustrous dark-brown coloration.

Example 3

Cationic Aerosol Colorant in Gel Form 1.300 g hydroxyethylcellulose6.000 g of cocamidopropylbetaine 2.000 g of polyethylene glycol 300capryl glyceride (Softigen ® 767) 3.000 g of decyl glucoside(Plantaren ® 2000) 1.000 g of cetyltrimethylammonium chloride 5.000 g ofisopropanol 0.200 g of ascorbic acid 0.100 g of disodiumethylenediaminetetraacetate 2.000 g of 2,5-diaminotoluene sulfate 0.750g of resorcinol 0.700 g of 2-amino-4-(2′-hydroxyethylamino)anisole 0.350g of 3-aminophenol 5.800 g of monoethanolamine 0.300 g of((4-ethyl((2-hydroxyethyl)amino)-2- nitrophenyl)amino)ethanol hydro-chloride (HC Blue No. 12) 1.000 g of 2,2′-((4-((2-hydroxyethyl)amino)-3-nitrophenyl)imino)bis-ethanol (HC Blue No. 2) 0.400 g of3-{[2-nitro-4-(trifluoromethyl)phenyl]amino}- 1,2-propanediol (HC YellowNo. 6) 0.013 g of 2,6-diamino-3-[(pyridin-3-yl)azo]pyridine 0.170 g of3-hydroxy-4-[(2-hydroxy-1-naphthalenyl)azo]-7-nitro-1-naphthalene-sulfonic acid monosodium salt (Acid Black No. 52)0.066 g of 3-(4-amino-2-chloro-5-nitrophenyl)amino- 1,2-propanediol (HCRed No. 10 + 11) 0.500 g of perfume oil to 100.000 g water

The gel base prepared by the cold-mixing method was combined with thehot-dissolved dyes and introduced into an appropriate compressed-gascontainer with propane/butane and F 152 (1:1 ratio) in an activeingredient/gas propellant ratio of 95:5%. The aerosol foam was appliedto dry hair and after an exposure time of 30 minutes rinsed out withwater. The hair was then dried. This gave a lustrous black coloration.

Example 4

Liquid Air Oxidation Colorant 2.50 g of oleic acid 2.00 g of cetearylalcohol 4.00 g of Undeceth-3 5.00 g of ethanol 2.50 g ofaminomethylpropanol 0.43 g of 2,5-diaminotoluene sulfate 0.47 g ofresorcinol 0.31 g of 2-methylresorcinol 1.59 g of 4-amino-3-methylphenol1.01 g of 5-amino-2-methylphenol 0.30 g of2,2′-((4-((2-hydroxyethyl)amino)-3- nitrophenyl)imino)bis-ethanol (HCBlue No. 2) 0.30 g of 3-(4-amino-2-chloro-5-nitrophenyl)amino-1,2-propanediol (HC Red No. 10 + 11) 0.20 g of2-amino-6-chloro-4-nitrophenol to 100.00 g water

The colorant was applied to dry hair and after an exposure time of 20minutes rinsed out with water. The hair was then dried. This gave alustrous garnet-red coloration.

Unless otherwise indicated, all percentages are by weight.

1. An aqueous or aqueous-alcoholic agent for coloring keratin fibers,said aqueous-alcoholic agent comprising a combination oxidation dyes andat least three direct dyes; wherein a quantitative ratio of saidoxidation dyes to said direct dyes is from 5:1 to 0.5:1 and saiddye-containing preparation is free of chemical oxidants.
 2. The agent asdefined in claim 1, wherein said oxidation dyes are each selected fromthe group consisting of 2,5-diaminotoluene, 2,4-diaminophenoxyethanol,resorcinol, 2-methylresorcinol, m-aminophenol, 4-amino-3-methylphenol,4-amino-2-hydroxytoluene, 6-amino-3-methylphenol,2-amino-4-hydroxyethylaminoanisole, 1-naphthol,hydroxyethyl-3,4-methylenedioxyaniline, 2,5-diaminophenylethanol,N,N-bis(2-hydroxyethyl)-p-phenylenediamine, phenylmethylpyrazolone,1-hydroxyethyl-4,5-diaminopyrazole, and salts thereof.
 3. The agent asdefined in claim 1, wherein said at least three direct dyes are eachselected from the group consisting of hydroxyethyl-2-nitro-p-toluidine,2-hydroxyethylpicramic acid, 4-nitrophenylaminourea, Basic Violet 2,Disperse Violet 1, HC Blue No. 2, HC Blue No. 12, HC Red No. 13, HCYellow No. 6, HC Red No. 3,4-amino-3-nitrophenol,4-[(2-hydroxyethyl)amino]-3-nitrophenol, HC Red No. 10, HC Red No. 11,2-chloro-6-ethylamino-4-nitrophenol, 2-amino-6-chloro-4-nitrophenol, HCYellow, No. 13, Basic Blue No. 99, Basic Brown No. 16, Basic Brown No.17, Basic Red No. 76, Basic Yellow No. 57,2,6-diamino-3-[(pyridin-3-yl)-azo]-pyridine and salts thereof.
 4. Theagent as defined in claim 1, wherein the agent further comprises atleast one alcohol selected from the group consisting of ethanol,isopropanol, n-propanol, glycerol, and 1,2-polyethylene glycol.
 5. Theagent as defined in claim 1, consisting of a hair colorant.
 6. A methodfor coloring keratin fibers, said method comprising the steps of: a)providing an aqueous or aqueous-alcoholic dye-containing preparationcomprising a combination oxidation dyes and at least three direct dyes,in which a quantitative ratio of said oxidation dyes to said direct dyesis from 5:1 to 0.5:1, said dye-containing preparation being free ofchemical oxidants; b) applying said aqueous or aqueous-alcoholicdye-containing preparation of step a) to the keratin fibers; c) afterapplying of step b), allowing said aqueous or aqueous-alcoholicdye-containing preparation to act on the keratin fibers for an exposuretime of from 5 to 60 minutes; and d) after the exposure time of step c),rinsing said aqueous or aqueous-alcoholic dye-containing preparationfrom the keratin fibers with water and then drying the keratin fibers;said method being performed without addition of any said chemicaloxidants.
 7. The method as defined in claim 6, further comprisingwashing the keratin fibers with a shampoo and then rinsing with saidwater before the keratin fibers are dried.
 8. The method as defined inclaim 6, wherein air oxidation of said oxidation dyes occurs while saidaqueous-alcoholic dye-containing preparation acts on the keratin fibers.9. The method as defined in claim 6, wherein said keratin fibers consistof hair.
 10. The method as defined in claim 6, wherein said oxidationdyes are each selected from the group consisting of 2,5-diaminotoluene,2,4-diaminophenoxyethanol, resorcinol, 2-methylresorcinol,m-aminophenol, 4-amino-3-methylphenol, 4-amino-2-hydroxytoluene,6-amino-3-methylphenol, 2-amino-4-hydroxyethylaminoanisole, 1-naphthol,hydroxyethyl-3,4-methylenedioxyaniline, 2,5-diaminophenylethanol,N,N-bis(2-hydroxyethyl)-p-phenylenediamine, phenylmethylpyrazolone,1-hydroxyethyl-4,5-diaminopyrazole and salts thereof.
 11. The method asdefined in claim 6, wherein said at least three direct dyes are eachselected from the group consisting of hydroxyethyl-2-nitro-p-toluidine,2-hydroxyethylpicramic acid, 4-nitrophenylaminourea, Basic Violet 2,Disperse Violet 1, HC Blue No. 2, HC Blue No. 12, HC Red No. 13, HCYellow No. 6, HC Red No. 3,4-amino-3-nitrophenol,4-[(2-hydroxyethyl)amino]-3-nitrophenol, HC Red No. 10, HC Red No. 11,2-chloro-6-ethylamino-4-nitrophenol, 2-amino-6-chloro-4-nitrophenol, HCYellow, No. 13, Basic Blue No. 99, Basic Brown No. 16, Basic Brown No.17, Basic Red No. 76, Basic Yellow No. 57,2,6-diamino-3-[(pyridin-3-yl)-azo]-pyridine and salts thereof.
 12. Themethod as defined in claim 6, wherein said dye-containing preparationcomprises at least one alcohol selected from the group consisting ofethanol, isopropanol, n-propanol, glycerol and 1,2-polyethylene glycol.13. A process of preparing an aqueous or aqueous-alcoholicdye-containing preparation for coloring keratin fibers, said processcomprising adding a combination of oxidation dyes and at least threedirect dyes to an aqueous or aqueous-alcoholic composition that is freeof chemical oxidants so as to form said aqueous or aqueous-alcoholicdye-containing preparation for coloring the keratin fibers that does notcontain any chemical oxidants; wherein a quantitative ratio of saidoxidation dyes to said direct dyes in said aqueous or aqueous-alcoholicdye-containing preparation is from 5:1 to 05:1 and wherein said aqueousor aqueous-alcoholic dye-containing preparation is free of chemicaloxidants.
 14. The process as defined in claim 13, wherein said aqueousor aqueous-alcoholic preparation contains at least one alcohol selectedfrom the group consisting of ethanol, isopropanol, n-propanol, glyceroland 1,2-polyethylene glycol.
 15. An aqueous or aqueous-alcoholic agentfor coloring keratin fibers, said agent comprising a combination ofoxidation dyes and at least three direct dyes; wherein said oxidationdyes are each selected from the group consisting of 2,5-diaminotoluene,2,4-diaminophenoxyethanol, resorcinol, 2-methylresorcinol,m-aminophenol, 4-amino-3-methylphenol, 4-amino-2-hydroxytoluene,6-amino-3-methylphenol, 2-amino-4-hydroxyethylaminoanisole, 1-naphthol,hydroxyethyl-3,4-methylenedioxyaniline, 2,5-diaminophenylethanol,N,N-bis(2-hydroxyethyl)-p-phenylenediamine, phenylmethylpyrazolone,1-hydroxyethyl-4,5-diaminopyrazole and salts thereof; and wherein saidat least three direct dyes are each selected from the group consistingof hydroxyethyl-2-nitro-p-toluidine, 2-hydroxyethylpicramic acid,4-nitrophenylaminourea, Basic Violet 2, Disperse Violet 1, HC Blue No.2, HC Blue No. 12, HC Red No. 13, HC Yellow No. 6, HC Red No.3,4-amino-3-nitrophenol, 4-[(2-hydroxyethyl)amino]-3-nitrophenol, HC RedNo. 10, HC Red No. 11, 2-chloro-6-ethylamino-4-nitrophenol,2-amino-6-chloro-4-nitrophenol, HC Yellow, No. 13, Basic Blue No. 99,Basic Brown No. 16, Basic Brown No 17, Basic Red No. 76, Basic YellowNo. 57, 2,6-diamino-3-[(pyridin-3-yl)-azo]-pyridine, and salts thereof;and wherein a quantitative ratio of said oxidation dyes to said directdyes is from 5:1 to 0.5:1 and said dye-containing preparation is free ofchemical oxidants.
 16. A method of coloring keratin fibers, said methodsaid method comprising the steps of: a) providing an aqueous oraqueous-alcoholic dye-containing preparation, said dye-containingpreparation comprising a combination of oxidation dyes and at leastthree direct dyes, in which a quantitative ratio of said oxidation dyesto said direct dyes is from 5:1 to 0.5:1, said dye-containingpreparation being free of chemical oxidants; b) applying said aqueous oraqueous-alcoholic dye-containing preparation of step a) to the keratinfibers; c) after applying of step b), allowing said aqueous oraqueous-alcoholic dye-containing preparation to act on the keratinfibers for an exposure time of from 5 to 60 minutes; and d) after theexposure time of step c), rinsing said aqueous or aqueous-alcoholicdye-containing preparation from the keratin fibers with water and thendrying the keratin fibers; wherein said method is performed withoutaddition of any of said chemical oxidants; wherein said oxidation dyesare each selected from the group consisting of 2,5-diaminotoluene,2,4-diaminophenoxyethanol, resorcinol, 2-methylresorcinol,m-aminophenol, 4-amino-3-methylphenol, 4-amino-2-hydroxytoluene,6-amino-3-methylphenol, 2-amino-4-hydroxyethylaminoanisole, 1-naphthol,hydroxyethyl-3,4-methylenedioxyaniline, 2,5-diaminophenylethanol,N,N-bis(2-hydroxyethyl)-p-phenylenediamine, phenylmethylpyrazolone,1-hydroxyethyl-4,5-diaminopyrazole, and salts thereof; and wherein saidat least three direct dyes are each selected from the group consistingof hydroxyethyl-2-nitro-p-toluidine 2-hydroxyethylpicramic acid,4-nitrophenylaminourea, Basic Violet 2, Disperse Violet 1, HC Blue No.2, HC Blue No. 12, HC Red No. 13, HC Yellow No. 6, HC Red No.3,4-amino-3-nitrophenol, 4-[(2-hydroxyethyl)amino]-3-nitrophenol, HC RedNo. 10, HC Red No. 11, 2-chloro-6-ethylamino-4-nitrophenol,2-amino-6-chloro-4-nitrophenol, HC Yellow, No. 13, Basic Blue No. 99,Basic Brown No. 16, Basic Brown No. 17, Basic Red No. 76, Basic YellowNo. 57, 2,6-diamino-3-[(pyridin-3-yl)-azo]-pyridine, and salts thereof.